Alkyl ether compositions and methods of use

ABSTRACT

A polymer includes a linker represented by Formula I ([OR 1 OCH 2 OR 2 OCH 2 ] m ), where R 1  and R 2  are, independently, alkylene, alkenylene, arylene, heteroarylene, or alkylarylalkylene; and the polymer has a weight average molecular weight of about 500 g/mol to about 2,000,000 g/mol, and m is 1 to 1000.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims the benefit of International Application SerialNo. PCT/US2012/048980, filed on Jul. 31, 2012, the entire disclosure ofwhich is hereby incorporated by reference for all purposes in itsentirety as if fully set forth herein.

FIELD

The present technology relates to polymers that are degradable andrecyclable and plastic materials that are made from such polymers.

BACKGROUND

The following description is provided to assist the understanding of thereader. None of the information provided or references cited is admittedto be prior art to the present technology.

Commercially relevant packaging materials are constantly evolving tomeet consumer demand for improved products by combining numerousphysical characteristics, such as flexibility, light weight, or strengthinto such packaging materials. Unfortunately, despite improvements inproduct performance, most of these commercially relevant packagingmaterials remain difficult or impractical to recycle. Unless it isbiodegradable, the discarded packaging materials accumulate in landfillsand waterways, where they may eventually harm ecosystems and wildlife.Consequently, the food packaging industry is seeking packaging materialsthat satisfy the evolving demands of consumers, yet can be more readilydegraded and recycled.

SUMMARY

The present technology provides for a recyclable polymer that includesmonomers joined by acid-sensitive —OCH₂O— linkers that can be cleavedupon exposure to acidic conditions. The recyclable polymer, havingmonomers joined by acid-sensitive —OCH₂O— linkers, can be incorporatedinto plastic materials such as, for example, food packaging or consumerpackaging materials. After the plastic materials have been used by aconsumer they can readily be degraded by subjecting the plasticmaterials to acidic conditions. Upon treatment with acid, the —OCH₂O—linkers within the polymers are hydrolyzed, the monomers are released,and the plastic materials are thus degraded. The resulting monomers canbe recombined with additional acid-sensitive —OCH₂O— linkers toregenerate the polymer and recycle the plastic materials.

In one aspect a polymer is provided including a linker represented byFormula I:

In Formula I, R¹ and R² are, independently, alkylene, alkenylene,arylene, heteroarylene, or alkylarylalkylene. In some embodiments, thepolymer has a weight average molecular weight of about 500 g/mol toabout 2,000,000 g/mol, and m is 1 to 1000. In some embodiments, R¹ isC₂-C₁₀ alkylene; and R² is a mixture of at least two of p-xylenyl,m-xylenyl, and o-xylenyl.

In another aspect a polymer is provided including a linker representedby Formula II:

In Formula II, R¹, R², and R³ are, independently, alkylene, alkenylene,arylene, heteroarylene, or alkylarylalkylene; and R¹ and R³ aredifferent. In some embodiments, the polymer has a weight averagemolecular weight of about 500 g/mol to about 2,000,000 g/mol. In someembodiments, R¹, R², or R³ is a mixture of at least two of p-xylenyl,m-xylenyl, and o-xylenyl.

In another aspect a polymer is provided, the polymer represented byFormula III.

In Formula III, R¹ and R² are, independently, alkylene, alkenylene,arylene, heteroarylene, or alkylarylalkylene; A is hydrogen, alkyl, or—C(O)R⁴; R⁴ is hydrogen, alkyl, or phenyl; PG^(1a) is the polymerizationproduct of a polymerization group PG¹; and PG¹ is acrylyl, methacrylyl,isocycanyl, styrenyl, epoxyl, vinyl, oxetanyl, DL-lactidyl, orbicyclo[2.2.1]hept-2-enyl. In some embodiments, the polymer has a weightaverage molecular weight of about 500 g/mol to about 2,000,000 g/mol; mis 1 to 1000; and q is 1 to 1000. In some embodiments, R¹ is C₂-C₁₀alkylene; and R² is a mixture of at least two of p-xylenyl, m-xylenyl,and o-xylenyl.

In another aspect a polymer is provided, where the polymer isrepresented by Formula IV:

In Formula IV, R¹ and R² are, independently, alkylene, alkenylene,arylene, heteroarylene, or alkylarylalkylene; R⁵ is hydrogen, CN, alkyl,or phenyl; A is hydrogen, alkyl, or —C(O)R⁴; and R⁴ is hydrogen, alkyl,or phenyl. In some embodiments, the polymer has a weight averagemolecular weight of about 500 g/mol to about 2,000,000 g/mol; m is 1 to1000; and q is 1 to 1000. In some embodiments, R¹ is C₂-C₁₀ alkylene;and R² is a mixture of at least two of p-xylenyl, m-xylenyl, ando-xylenyl.

A method is provided for preparing polymer represented by Formula III.The method includes contacting XCH₂OR²OCH₂X with HOR¹OH, HOR¹OA, and abase to form a polymer represented by Formula V

contacting the polymer represented by Formula V with a compoundrepresented by PG¹-L and a base to form a polymer represented by FormulaVI:

andpolymerizing PG¹ of the polymer represented by Formula VI to form thepolymer represented by Formula III:

In Formulae III, V, and VI, R¹ and R² are, independently, alkylene,alkenylene, arylene, heteroarylene, or alkylarylalkylene; R⁴ ishydrogen, alkyl, or phenyl; A is hydrogen, alkyl, or —C(O)R⁴; X is aleaving group; PG¹ is a polymerizable group that is acrylyl,methacrylyl, isocycanyl, styrenyl, epoxyl, vinyl, oxetanyl, DL-lactidyl,or bicyclo[2.2.1]hept-2-enyl; PG^(1a) is the polymerization product ofthe polymerizable group PG¹; L is a leaving group; m is 1 to 1000; and qis 1 to 1000. In some embodiments, R¹ is C₂-C₁₀ alkylene; and R² is amixture of at least two of p-xylenyl, m-xylenyl, and o-xylenyl.

In another aspect, a method is provided for degrading a polymer, wherethe method includes providing a polymer including a linker representedby Formula I, contacting the polymer with acid; and obtaining acomposition including HOR¹OH and HOR²OH.

The foregoing summary is illustrative only and is not intended to be inany way limiting. In addition to the illustrative aspects, embodimentsand features described above, further aspects, embodiments and featureswill become apparent by reference to the following drawings and thedetailed description.

DETAILED DESCRIPTION

The illustrative embodiments described in the detailed description andclaims are not meant to be limiting. Other embodiments may be utilized,and other changes may be made, without departing from the spirit orscope of the subject matter presented here.

The present technology is described herein using several definitions, asset forth throughout the specification.

As used herein, unless otherwise stated, the singular forms “a,” “an,”and “the” include plural reference. Thus, for example, a reference to “acell” includes a plurality of cells, and a reference to “a molecule” isa reference to one or more molecules.

As used herein, “about” will be understood by persons of ordinary skillin the art and will vary to some extent depending upon the context inwhich it is used. If there are uses of the term which are not clear topersons of ordinary skill in the art, given the context in which it isused, “about” will mean up to plus or minus 10% of the particular term.

Alkyl groups include straight chain, branched chain, or cyclic alkylgroups having 1 to 24 carbons or the number of carbons indicated herein.In some embodiments, an alkyl group has 1 to 16 carbon atoms, 1 to 12carbons, 1 to 8 carbons or, in some embodiments, 1 to 6, or 1, 2, 3, 4or 5 carbon atoms. Examples of straight chain alkyl groups includegroups such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl,n-heptyl, and n-octyl groups. Examples of branched alkyl groups include,but are not limited to, isopropyl, iso-butyl, sec-butyl, tert-butyl,neopentyl, isopentyl, and 2,2-dimethylpropyl groups. In someembodiments, the alkyl groups may be substituted alkyl groups.

Heteroalkyl groups include alkyl groups, as defined herein, substitutedby one or more O, N, or S atoms.

Cycloalkyl groups are cyclic alkyl groups having 3 to 10 carbon atoms.In some embodiments, the cycloalkyl group has 3 to 7 ring members,whereas in other embodiments the number of ring carbon atoms range from3 to 5, 3 to 6, or 5, 6 or 7. Cycloalkyl groups further includemonocyclic, bicyclic and polycyclic ring systems. Monocyclic groupsinclude, e.g., cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, andcycloheptyl groups. Bicyclic and polycyclic cycloalkyl groups includebridged or fused rings, such as, but not limited to,bicyclo[3.2.1]octane, decalinyl, and the like. Cycloalkyl groups includerings that are substituted with straight or branched chain alkyl groupsas defined above. In some embodiments, the cycloalkyl groups aresubstituted cycloalkyl groups. Representative substituted alkenyl groupsmay be mono-substituted or substituted more than once, such as, but notlimited to, mono-, di- or tri-substituted with substituents such asthose listed above. Representative substituted alkyl groups may bemono-substituted or substituted more than once, such as, but not limitedto, mono-, di- or tri-substituted with substituents such as those listedabove.

Alkenyl groups include straight and branched chain alkyl groups asdefined above, except that at least one double bond exists between twocarbon atoms. Thus, alkenyl groups have 2 to 24 carbon atoms, andtypically 2 to 10 carbons or, in some embodiments, 2 to 8, 2 to 6, or 2to 4 carbon atoms. Examples include, but are not limited to vinyl,allyl, —CH═CH(CH₃), —CH═C(CH₃)₂, —C(CH₃)═CH₂, —C(CH₃)═CH(CH₃),—C(CH₂CH₃)═CH₂, among others. Representative substituted alkenyl groupsmay be mono-substituted or substituted more than once, such as, but notlimited to, mono-, di- or tri-substituted with substituents such asthose listed above.

The terms “alkylene,” “cycloalkylene,” “alkenylene,” “arylene,”“heteroarylene,” and “alkylarylalkylene” alone or as part of anothersubstituent means a divalent radical derived from an alkyl, cycloalkyl,alkenyl, aryl, heteroaryl, or alkylarylalkyl group, respectively, asexemplified by —CH₂CH₂CH₂CH₂—. For alkylene, cycloalkylene, alkenylene,arylene, heteroarylene, and alkylarylalkylene linking groups, noorientation of the linking group is implied.

The term “amine” (or “amino”) as used herein refers to —NHR and —NRR′groups, where R, and R′ are independently hydrogen, or a substituted orunsubstituted alkyl, alkenyl, alkynyl, cycloalkyl, aryl or aralkyl groupas defined herein. Examples of amino groups include NH₂, methylamino,dimethylamino, ethylamino, diethylamino, propylamino, isopropylamino,phenylamino, benzylamino, and the like.

The term “oxo” refers to a divalent oxygen group. While the termincludes doubly bonded oxygen, such as that found in a carbonyl group,as used herein, the term oxo explicitly includes singly bonded oxygen ofthe form —O— which is part of a polymer backbone. Thus, an oxo group maybe part of an ether linkage (—O—), an ester linkage (—O—C(O)—), acarbonate linkage (—O—C(O)O—), a carbamate linkage (—O—C(O)NH— or—O—C(O)NR—), and the like.

“Substituted” refers to a chemical group as described herein thatfurther includes one or more substituents, such as lower alkyl(including substituted lower alkyl such as haloalkyl, hydroxyalkyl,aminoalkyl), aryl (including substituted aryl), acyl, halogen, hydroxy,amino, alkoxy, alkylamino, acylamino, thioamido, acyloxy, aryloxy,aryloxyalkyl, carboxy, thiol, sulfide, sulfonyl, oxo, both saturated andunsaturated cyclic hydrocarbons (e.g., cycloalkyl, cycloalkenyl),cycloheteroalkyls and the like. These groups may be attached to anycarbon or substituent of the alkyl, alkenyl, alkynyl, aryl,cycloheteroalkyl, alkylene, alkenylene, alkynylene, arylene,heteroarylene, hetero moieties. Additionally, the substituents may bependent from, or integral to, the carbon chain itself.

The present technology provides for polymers containing —OCH₂O— linkermoieties that render the polymers chemically stable during commercialuse but easily cleaved upon exposure to conditions (e.g., acidicconditions) not typically encountered during commercial use. The —OCH₂O—linker moieties can be combined with various monomers to tune thephysical characteristics (e.g., flexibility, hardness, softness, etc.)of the polymer. The polymers described herein, having acid-sensitive—OCH₂O— linkers, are more readily degraded with acid and recycled thanpolymers made from conventional polymers e.g., those made from PET,polyethylene, or polypropylene. The polymers can be incorporated inpackaging materials that can be readily degraded to monomeric startingmaterials following commercial use. Further, the monomeric startingmaterials that can readily be resynthesized (i.e., recycled) into thepolymers described herein. Packaging made from the polymers describedherein is cost effective, convenient, and light weight.

The polymers described herein can be used to make packaging, containers,and plastic goods for any application. For example, the polymersdescribed herein can be used in wide variety of plastics for anyapplication such as food, beverage, or consumer packaging, sport drinkbottles, freeze vacuum containers, shipping cartons, bags, opticallenses, utensils, plates, toys, furniture coatings, automobile plasticcomponents, fiberglass, cookware, plastic utensils, computers (e.g.,tablets, laptops, netbooks) computer components, medical implants,mobile electronics, phones, calculators, paneling, coatings, fibers,insulation, seats, tables, shelves, table tops, counters, caulking andthe like. The polymers described herein can also be used in aviationcomponents.

As noted above, the polymers include a —OCH₂O— group. This group may beincorporated into a linker represented by Formula I:

In Formula I, R¹ and R² are, independently, alkylene, alkenylene,arylene, heteroarylene, or alkylarylalkylene; the polymer has a weightaverage molecular weight of about 500 g/mol to about 2,000,000 g/mol,and m is 1 to 1000.

In Formula I, R¹ and R² are groups that are joined by the —OCH₂O—moieties. Each R¹ and R² group can be selected to tune the physicalcharacteristics (e.g., flexibility, hardness, softness, etc.) of thepolymer to accommodate the intended application (e.g., food packaging,consumer packaging, etc.) for the polymer. For example, flexiblepolymers generally include flexible alkyl groups at R¹ and/or R²,whereas the polymer can be made more rigid by incorporating inflexiblearyl groups at R¹ and/or R². Flexible groups impart “flexibility” and“softness” to the polymer, while rigid groups impart “rigidity” and“hardness.” Such terms, while relative, are widely used in the art andare well-understood terms of distinction.

For example, R¹ may be alkylene in Formula I. In some embodiments, R¹ isC₂-C₁₀ alkylene. In some embodiments, R¹ is (CH₂)₂; (CH₂)₄; (CH₂)₆; or(CH₂)₈. In some embodiments, R¹ is (CH₂)₄. R¹ may be alkenylene. In someembodiments, R¹ is C₂-C₁₀ alkenylene. In some embodiments, R¹ isvinylene or allylene. R¹ may be arylene. In some embodiments, R¹ isphenylene, biphenylene, anthracenlyene, or naphthalenylene. R¹ may alsobe alkylarylalkylene. In some embodiments, R¹ is

Further, R² may be alkylene in Formula I. In some embodiments, R² isC₂-C₁₀ alkylene. In some embodiments, R² is (CH₂)₂; (CH₂)₄; (CH₂)₆; or(CH₂)₈. In some embodiments, R² is (CH₂)₄. R² may be alkenylene. In someembodiments, R² is C₂-C₁₀ alkenylene. In some embodiments, R² isvinylene or allylene. R² may be arylene. In some embodiments, R² isphenylene, biphenylene, anthracenlyene, or naphthalenylene. R² may alsobe alkylarylalkylene. In some embodiments, R² is p-xylenyl, m-xylenyl,or o-xylenyl.

In Formula I, each R¹ and R² can independently be a mixture of groups.For example, each R¹ and R² can independently be a mixture of at leasttwo of p-xylenyl, m-xylenyl, and o-xylenyl, where p-xylenyl groups, forexample, can add rigidity to the polymer, whereas m-xylenyl groups, forexample, can decrease the rigidity of the polymer.

In some embodiments, R¹ is C₂-C₁₀ alkylene; and R² is a mixture of atleast two of p-xylenyl, m-xylenyl, and o-xylenyl. In some embodiments,R² is a mixture of p-xylenyl and m-xylenyl having a p-xylenyl:m-xylenylratio of about 2:1 to about 20:1. In some embodiments, R² is a mixtureof p-xylenyl and m-xylenyl having a p-xylenyl:m-xylenyl ratio of about5:1, 10:1, or 15:1. In some embodiments, R² is a mixture of p-xylenyland o-xylenyl having a p-xylenyl:o-xylenyl ratio of about 2:1 to about20:1. In some embodiments, R² is a mixture of p-xylenyl and o-xylenylhaving a p-xylenyl:o-xylenyl ratio of about 5:1, 10:1, or 15:1.

The polymers of Formula I have a weight average molecular weight (Mw) ofabout 500 g/mol to about 2,000,000 g/mol. This may include an Mw ofabout 500 g/mol to about 500,000 g/mol, about 500 g/mol to about 100,000g/mol, about 500 g/mol to about 50,000 g/mol, or about 500 g/mol toabout 10,000 g/mol. Specific examples of Mw include about 500 g/mol,about 1,000 g/mol, about 5,000 g/mol, about 10,000 g/mol, about 20,000g/mol, about 30,000 g/mol, about 40,000 g/mol, about 50,000 g/mol, about60,000 g/mol, about 70,000 g/mol, about 80,000 g/mol, about 90,000g/mol, about 100,000 g/mol, about 200,000 g/mol, about 250,000 g/mol,about 500,000 g/mol, about 750,000 g/mol, about 1,000,000 g/mol, about2,000,000 g/mol, and ranges between any two of these values.

In some embodiments, m in Formula I is 1 to 1,000, 1 to 500, 1 to 250, 1to 100, 1 to 50, or 1 to 10. Specific examples of m include 1, 2, 3, 4,5, 6, 7, 8, 9, 10, 15, 20, 25, 30, 35, 40, 45, 50, 60, 70, 80, 90, 100,200, 250, 300, 400, 500, 750, 1,000, and ranges between any two of thesevalues.

In accordance with another aspect a polymer is provided, where thepolymer includes a linker represented by Formula II:

In Formula II, R¹, R², and R³ are, independently, alkylene, alkenylene,arylene, heteroarylene, or alkylarylalkylene; R¹ and R³ are different;the polymer has a weight average molecular weight of about 500 g/mol toabout 2,000,000 g/mol, and m is 1 to 1000.

In Formula II, R¹ may be alkylene. In some embodiments, R¹ is C₂-C₁₀alkylene. In some embodiments, R¹ is (CH₂)₂; (CH₂)₄; (CH₂)₆; or (CH₂)₈.In some embodiments, R¹ is (CH₂)₄. R¹ may be alkenylene. In someembodiments, R¹ is C₂-C₁₀ alkenylene. In some embodiments, R¹ isvinylene or allylene. R¹ may be arylene. In some embodiments, R¹ isphenylene, biphenylene, anthracenlyene, or naphthalenylene. R¹ may alsobe alkylarylalkylene. In some embodiments, R¹ is p-xylenyl, m-xylenyl,or o-xylenyl.

R² may be alkylene in Formula II. In some embodiments, R² is C₂-C₁₀alkylene. In some embodiments, R² is (CH₂)₂; (CH₂)₄; (CH₂)₆; or (CH₂)₈.In some embodiments, R² is (CH₂)₄. R² may be alkenylene. In someembodiments, R² is C₂-C₁₀ alkenylene. In some embodiments, R² isvinylene or allylene. R² may be arylene. In some embodiments, R² isphenylene, biphenylene, anthracenlyene, or naphthalenylene. R² may alsobe alkylarylalkylene. In some embodiments, R² is p-xylenyl, m-xylenyl,or o-xylenyl.

R³ may be alkylene in Formula II. In some embodiments, R³ is C₂-C₁₀alkylene. In some embodiments, R³ is (CH₂)₂; (CH₂)₄; (CH₂)₆; or (CH₂)₈.In some embodiments, R³ is (CH₂)₄. R³ may be alkenylene. In someembodiments, R³ is C₂-C₁₀ alkenylene. In some embodiments, R³ isvinylene or allylene. R³ may be arylene. In some embodiments, R³ isphenylene, biphenylene, anthracenlyene, or naphthalenylene. R³ may alsobe alkylarylalkylene. In some embodiments, R³ is p-xylenyl, m-xylenyl,or o-xylenyl. In some embodiments, R¹, R², or R³ is a mixture of atleast two of p-xylenyl, m-xylenyl, and o-xylenyl.

In some embodiments, the polymer has a weight average molecular weight(Mw) of about 500 g/mol to about 2,000,000, 500 g/mol to about 1,000,000g/mol, about 500 g/mol to about 500,000 g/mol, about 500 g/mol to about100,000 g/mol, about 500 g/mol to about 50,000 g/mol, or about 500 g/molto about 10,000 g/mol. Specific examples of Mw include about 500 g/mol,about 1,000 g/mol, about 5,000 g/mol, about 10,000 g/mol, about 20,000g/mol, about 30,000 g/mol, about 40,000 g/mol, about 50,000 g/mol, about60,000 g/mol, about 70,000 g/mol, about 80,000 g/mol, about 90,000g/mol, about 100,000 g/mol, about 200,000 g/mol, about 250,000 g/mol,about 500,000 g/mol, about 750,000 g/mol, about 1,000,000 g/mol, andranges between any two of these values. In some embodiments, m is 1 to500, 1 to 250, 1 to 100, 1 to 50, or 1 to 10. Specific examples of minclude 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 15, 20, 25, 30, 35, 40, 45, 50,60, 70, 80, 90, 100, 200, 300, 400, 500, and ranges between any two ofthese values.

In some embodiments, R¹ and R³ are alkylene; and R² isalkylarylalkylene. In some embodiments, R¹ and R³ are alkylarylalkylene;and R² is alkylene. In some embodiments, each alkylarylalkylene is amixture of at least two of p-xylenyl, m-xylenyl, and o-xylenyl.

In some embodiments, each alkylarylalkylene is, independently, a mixtureof p-xylenyl and m-xylenyl having a p-xylenyl:m-xylenyl ratio of about2:1 to about 20:1. In some embodiments, each alkylarylalkylene is,independently, a mixture of p-xylenyl and o-xylenyl having ap-xylenyl:o-xylenyl ratio of about 2:1 to about 20:1. In someembodiments, each alkylene is C₁-C₁₀ alkylene. In some embodiments, eachalkylene is (CH₂)₂; (CH₂)₄; (CH₂)₆; or (CH₂)₈.

The linkers described above may be the entire, stand-alone polymer, orthe linker may be incorporated into other polymers. For example, thepolymer may be represented by Formula III:

In Formula III, R¹ and R² are, independently, alkylene, alkenylene,arylene, heteroarylene, or alkylarylalkylene; A is hydrogen, alkyl, or—C(O)R⁴; R⁴ is hydrogen, alkyl, or phenyl; PG^(1a) is the polymerizationproduct of a polymerization group PG¹; PG¹ is acrylyl, methacrylyl,isocycanyl, styrenyl, epoxyl, vinyl, oxetanyl, DL-lactidyl, orbicyclo[2.2.1]hept-2-enyl; the polymer has a weight average molecularweight of about 500 g/mol to about 2,000,000 g/mol; m is 1 to 1000; andq is 1 to 1000.

In Formula III, R¹ may be alkylene. In some embodiments, R¹ is C₂-C₁₀alkylene. In some embodiments, R¹ is (CH₂)₂; (CH₂)₄; (CH₂)₆; or (CH₂)₈.In some embodiments, R¹ is (CH₂)₄. R¹ may be alkenylene. In someembodiments, R¹ is C₂-C₁₀ alkenylene. In some embodiments, R¹ isvinylene or allylene. R¹ may be arylene. In some embodiments, R¹ isphenylene, biphenylene, anthracenlyene, or naphthalenylene. R¹ may alsobe alkylarylalkylene. In some embodiments, R¹ is p-xylenyl, m-xylenyl,or o-xylenyl.

R² may be alkylene in Formula III. In some embodiments, R² is C₂-C₁₀alkylene. In some embodiments, R² is (CH₂)₂; (CH₂)₄; (CH₂)₆; or (CH₂)₈.In some embodiments, R² is (CH₂)₄. R² may be alkenylene. In someembodiments, R² is C₂-C₁₀ alkenylene. In some embodiments, R² isvinylene or allylene. R² may be arylene. In some embodiments, R² isphenylene, biphenylene, anthracenlyene, or naphthalenylene. R² may alsobe alkylarylalkylene. In some embodiments, R² is p-xylenyl, m-xylenyl,or o-xylenyl.

In some embodiments, the polymer has a Mw of about 500 g/mol to about1,000,000. This may include an Mw of about 500 g/mol to about 500,000,about 500 g/mol to about 100,000, about 500 g/mol to about 50,000, orabout 500 g/mol to about 10,000. Specific examples of Mw include about500 g/mol, about 1,000 g/mol, about 5,000 g/mol, about 10,000 g/mol,about 20,000 g/mol, about 30,000 g/mol, about 40,000 g/mol, about 50,000g/mol, about 60,000 g/mol, about 70,000 g/mol, about 80,000 g/mol, about90,000 g/mol, about 100,000 g/mol, about 200,000 g/mol, about 250,000g/mol, about 500,000 g/mol, about 750,000 g/mol, about 1,000,000 g/mol,about 2,000,000, and ranges between any two of these values. In someembodiments, m is 1 to 500, 1 to 250, 1 to 100, 1 to 50, or 1 to 10.Specific examples of m include 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 15, 20,25, 30, 35, 40, 45, 50, 60, 70, 80, 90, 100, 200, 250, 300, 400, 500,750, 1,000,000, and ranges between any two of these values. Specificexamples of q include 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 15, 20, 25, 30, 35,40, 45, 50, 100, 200, 300, 400, 500, 600, 700, 800, 900, 1,000, andranges between any two of these values.

In accordance with another aspect a polymer is provided, where thepolymer is represented by Formula IV:

In Formula IV, R¹ and R² are, independently, alkylene, alkenylene,arylene, heteroarylene, or alkylarylalkylene; R⁵ is hydrogen, CN, alkyl,or phenyl; A is hydrogen, alkyl, or —C(O)R⁴; R⁴ is hydrogen, alkyl, orphenyl; the polymer has a weight average molecular weight of about 500g/mol to about 2,000,000 g/mol; m is 1 to 1000; and q is 1 to 1000.

In Formula IV, R¹ may be alkylene. In some embodiments, R¹ is C₂-C₁₀alkylene. In some embodiments, R¹ is (CH₂)₂; (CH₂)₄; (CH₂)₆; or (CH₂)₈.In some embodiments, R¹ is (CH₂)₄. R¹ may be alkenylene. In someembodiments, R¹ is C₂-C₁₀ alkenylene. In some embodiments, R¹ isvinylene or allylene. R¹ may be arylene. In some embodiments, R¹ isphenylene, biphenylene, anthracenlyene, or naphthalenylene. R¹ may alsobe alkylarylalkylene. In some embodiments, R¹ is p-xylenyl, m-xylenyl,or o-xylenyl.

R² may be alkylene in Formula IV. In some embodiments, R² is C₂-C₁₀alkylene. In some embodiments, R² is (CH₂)₂; (CH₂)₄; (CH₂)₆; or (CH₂)₈.In some embodiments, R² is (CH₂)₄. R² may be alkenylene. In someembodiments, R² is C₂-C₁₀ alkenylene. In some embodiments, R² isvinylene or allylene. R² may be arylene. In some embodiments, R² isphenylene, biphenylene, anthracenlyene, or naphthalenylene. R² may alsobe alkylarylalkylene. In some embodiments, R² is p-xylenyl, m-xylenyl,or o-xylenyl.

In some embodiments, the polymer has a weight average molecular weight(Mw) of about 500 g/mol to about 2,000,000, about 500 g/mol to about1,000,000, about 500 g/mol to about 500,000, about 500 g/mol to about100,000, about 500 g/mol to about 50,000, or about 500 g/mol to about10,000. Specific examples of Mw include about 500 g/mol, about 1,000g/mol, about 5,000 g/mol, about 10,000 g/mol, about 20,000 g/mol, about30,000 g/mol, about 40,000 g/mol, about 50,000 g/mol, about 60,000g/mol, about 70,000 g/mol, about 80,000 g/mol, about 90,000 g/mol, about100,000 g/mol, about 200,000 g/mol, about 250,000 g/mol, about 500,000g/mol, about 750,000 g/mol, about 1,000,000 g/mol, about 2,000,000, andranges between any two of these values. In some embodiments, m is 1 to50. In some embodiments, m is 1 to 40, 1 to 30, 1 to 20, 1 to 10, 1 to5. Specific examples of m include 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 15, 20,25, 30, 35, 40, 45, 50, 60, 70, 80, 90, 100, 200, 250, 300, 400, 500,750, 1,000,000, and ranges between any two of these values. In someembodiments, q is 1 to 50. In some embodiments, q is 1 to 40, 1 to 30, 1to 20, 1 to 10, or 1 to 5. Specific examples of q include 1, 2, 3, 4, 5,6, 7, 8, 9, 10, 15, 20, 25, 30, 35, 40, 45, 50, 100, 200, 300, 400, 500,600, 700, 800, 900, 1,000, and ranges between any two of these values.

In some embodiments, R¹ is (CH₂)₂; (CH₂)₄; (CH₂)₆; or (CH₂)₈; and R² isa mixture of at least two of p-xylenyl, m-xylenyl, and o-xylenyl.

The above polymers are amenable to forming into a wide variety ofarticles as introduced above. The polymers may be formed into articlesusing techniques such as blowing, compaction molding, compressionmolding, injection molding, extrusion, rotomolding, vacuum molding,thermoforming, and the like as are known in the art.

In accordance with another aspect a method is provided of preparingpolymer represented by Formula III where the method includes: contactingXCH₂OR²OCH₂X with HOR¹OH, HOR¹OA, and a base to form a polymerrepresented by Formula V

contacting the polymer represented by Formula V with a compoundrepresented by PG¹-L and a base to form a polymer represented by FormulaVI:

andpolymerizing PG¹ of the polymer represented by Formula VI to form thepolymer represented by Formula III:

In Formulae III, V, and VI, R¹ and R² are, independently, alkylene,alkenylene, arylene, heteroarylene, or alkylarylalkylene; A is hydrogen,alkyl, or C(O)R⁴; R⁴ is hydrogen, alkyl, or phenyl; X is a leavinggroup; PG¹ is a polymerizable group selected from the group consistingof acrylyl, methacrylyl, isocycanyl, styrenyl, epoxyl, vinyl, oxetanyl,DL-lactidyl, and bicyclo[2.2.1]hept-2-enyl; PG^(1a) is thepolymerization product of the polymerizable group PG¹; L is a leavinggroup; m is 1 to 1000; and q is 1 to 1000.

In Formula III, R¹ may be alkylene. In some embodiments, R¹ is C₂-C₁₀alkylene. In some embodiments, R¹ is (CH₂)₂; (CH₂)₄; (CH₂)₆; or (CH₂)₈.In some embodiments, R¹ is (CH₂)₄. R¹ may be alkenylene. In someembodiments, R¹ is C₂-C₁₀ alkenylene. In some embodiments, R¹ isvinylene or allylene. R¹ may be arylene. In some embodiments, R¹ isphenylene, biphenylene, anthracenlyene, or naphthalenylene. R¹ may alsobe alkylarylalkylene. In some embodiments, R¹ is p-xylenyl, m-xylenyl,or o-xylenyl.

R² may be alkylene in Formula III. In some embodiments, R² is C₂-C₁₀alkylene. In some embodiments, R² is (CH₂)₂; (CH₂)₄; (CH₂)₆; or (CH₂)₈.In some embodiments, R² is (CH₂)₄. R² may be alkenylene. In someembodiments, R² is C₂-C₁₀ alkenylene. In some embodiments, R² isvinylene or allylene. R² may be arylene. In some embodiments, R² isphenylene, biphenylene, anthracenlyene, or naphthalenylene. R² may alsobe alkylarylalkylene. In some embodiments, R² is p-xylenyl, m-xylenyl,or o-xylenyl.

In some embodiments, the polymer has a weight average molecular weight(Mw) of about 500 g/mol to about 2,000,000 g/mol, about 500 g/mol toabout 1,000,000 g/mol, about 500 g/mol to about 500,000 g/mol, about 500g/mol to about 100,000 g/mol, about 500 g/mol to about 50,000 g/mol, orabout 500 g/mol to about 10,000 g/mol. Specific examples of Mw includeabout 500 g/mol, about 1,000 g/mol, about 5,000 g/mol, about 10,000g/mol, about 20,000 g/mol, about 30,000 g/mol, about 40,000 g/mol, about50,000 g/mol, about 60,000 g/mol, about 70,000 g/mol, about 80,000g/mol, about 90,000 g/mol, about 100,000 g/mol, about 200,000 g/mol,about 250,000 g/mol, about 500,000 g/mol, about 750,000 g/mol, about1,000,000 g/mol, about 2,000,000, and ranges between any two of thesevalues.

In some embodiments, the polymer represented by Formula III is a polymerrepresented by Formula IV:

In Formula IV, R⁵ is hydrogen, CN, alkyl, or phenyl.

In some embodiments, the method further includes forming XCH₂OR²OCH₂X bycontacting R⁶OCH₂OR²OCH₂OR⁶ with HX, where R⁶ is alkyl. In someembodiments, R⁶ is methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl,or octyl

In some embodiments, X is Cl, Br, I,

In some embodiments, L is Cl, Br, I,

In some embodiments, X and L are both Cl.

In some embodiments, the base is a tertiary amine, secondary amine,pyridine, or a carbonate salt. In some embodiments, the base ismorpholine, N-methylmorpholine, piperidine, N-methypiperidine,piperazine, N-methylpiperazine, N,N-dimethylpiperazine, triethylamine,diisopropylethylamine, or pyridine.

In another aspect, a method is provided for degrading any of the abovepolymers, the method including providing the polymer, contacting thepolymer with acid, and obtaining a composition including alcoholdegradation products. For example, where the polymer is that of FormulaI, above, the alcohol degradation products will include HOR¹OH andHOR²OH. Where the polymer includes a further polymeric moiety orpolymerizable group, such as those represented in Formulas III, IV, andVI, the degradation products will include the polymer fragments as wellas the alcohol degradation products.

Because the polymers described above are originally prepared fromalcohols such as HOR¹OH and HOR²OH, the acid degradation provides againthe starting materials for the polymerization. Thus, at least in thesegments of the polymer which include R¹ and R² the regeneration of thestarting materials is realized. These materials may then be used to makeother polymers. Because the polymers are degraded into their originalstarting materials, the above polymers provide at least one advantageover other recycled plastics and polymers, that advantage being that therecycled (actually re-polymerized) polymers are the same as the originalpolymers. Other recycled plastics typically grinder the polymers intosmaller fragments, then treat the terminal groups to link together thesmaller fragments and oligomers. The present “recycled” polymers are tobe completely reconstructed from the original starting materials thatare recovered from the degradation process.

Illustrative acids for use in the methods of degrading include, but arenot limited to, HCl, HBr, H₂SO₄, acetic acid, trifluoroacetic acid,phosphoric acid, nitric acid, and combinations thereof. The acid may beadded as the neat acid to the polymer or as a diluted solution such asan aqueous solution. Such an aqueous acid solution can have any pH ofless than 7.0. Representative pH values for the acidic solution that isadded to the polymer may be <6.0, <5.0, <4.0, <3.0, <2.0, or <1.0.

The temperature of the degradation will impact the rate at which thedegradation occurs. Accordingly, a wide range of temperatures may beemployed. For example, the contacting may be conducted at a temperatureof about 20° C. to about 200° C. This will include temperatures of about20° C. to about 150° C., or about 20° C. to about 100° C., or about 20°C. to about 50° C. In some embodiments, the contacting is conducted atroom temperature.

The present technology, thus generally described, will be understoodmore readily by reference to the following Examples, which are providedby way of illustration and are not intended to be limiting of thepresent technology.

EXAMPLES Example 1 Synthesis of Representative Polymers

Polymer 1.1:

Butane-1,4-diol (1 mmol) and 1,4-bis(chloromethoxy)butane (1 mmol) arecombined in DMF (10 mL) with piperidine (2.5 mmol) and stirred 1 hour at60° C. Polymer 1.1 precipitates from solution and is washed with diluteaqueous HCl (0.1M), aqueous NaHCO₃, and water. Polymer 1.1 is expectedto be softer and more flexible than polymers 1.2 and 1.3, describedbelow. The softness, hardness, and flexibility of these polymers can bemeasured according to protocols known in the art, such as ASTM D4145-10Standard Test Method for Coating Flexibility of Prepainted Sheet, ASTMD1004-09 Standard Test Method for Tear Resistance (Graves Tear) ofPlastic Film and Sheeting, and ASTM D3892-93(2009) Standard Practice forPackaging/Packing of Plastics.

Polymer 1.2:

Ethane-1,2-diol (1 mmol) and 1,4-bis((chloromethoxy)methyl)benzene (1mmol) are combined in DMF (10 mL) with piperidine (2.5 mmol) and stirred1 hour at 60° C. Polymer 1.2 precipitates from solution and is washedwith dilute aqueous HCl (0.1M), aqueous NaHCO₃, and water. Polymer 1.2is expected to be harder and more rigid than polymers 1.1 and 1.3.

Polymer 1.3:

Ethane-1,2-diol (1 mmol), 1,3-bis((chloromethoxy)methyl)benzene (0.1mmol), and 1,4-bis((chloromethoxy)methyl)benzene (1 mmol) are combinedin DMF (10 mL) with piperidine (2.5 mmol) and stirred 1 hour at 60° C.Polymer 1.3 precipitates from solution and is washed with dilute aqueousHCl (0.1M), aqueous NaHCO₃, and water. Polymer 1.3 is expected to beharder and more rigid than polymers 1.1 but softer and more flexiblethan polymer 1.2.

Synthetic methods substantially similar to those shown above can be usedto make any of the polymers described herein.

Example 2 Degradation of Representative Polymers

Polymer 1.1 is treated with CH₂Cl₂ and gaseous HCl and stirred 3 hours.The reaction mixture is concentrated and the crude butane-1,4-diol canbe used directly in example 3 without further treatment or purification.

Example 3 Recycling of Representative Polymers

Polymer 1.1 is “recycled” by bubbling HCl gas into a mixture of crudebutane-1,4-diol (1 mmol) and formaldehyde (2.5 mmol). The crude1,4-bis(chloromethoxy)butane can be modified as shown in Example 1 toyield polymer 1.1.

The polymers described herein, such as those of Examples 1 and 2, haveacid-sensitive —OCH₂O— linkers, are more readily degraded with acid thanconventional polymers e.g., those made from PET, polyethylene, orpolypropylene. The polymers described herein, such as those of Example3, are also more easily recycled than conventional polymers.

EQUIVALENTS

The embodiments, illustratively described herein may suitably bepracticed in the absence of any element or elements, limitation orlimitations, not specifically disclosed herein. Thus, for example, theterms ‘comprising,’ ‘including,’ ‘containing,’ etc. shall be readexpansively and without limitation. Additionally, the terms andexpressions employed herein have been used as terms of description andnot of limitation, and there is no intention in the use of such termsand expressions of excluding any equivalents of the features shown anddescribed or portions thereof, but it is recognized that variousmodifications are possible within the scope of the claimed technology.Additionally, the phrase ‘consisting essentially of’ will be understoodto include those elements specifically recited and those additionalelements that do not materially affect the basic and novelcharacteristics of the claimed technology. The phrase ‘consisting of’excludes any element not specified.

The present disclosure is not to be limited in terms of the particularembodiments described in this application, which are intended asillustrations of various aspects. Many modifications and variations canbe made without departing from its spirit and scope, as will be apparentto those skilled in the art. Functionally equivalent compositions,apparatuses, and methods within the scope of the disclosure, in additionto those enumerated herein, will be apparent to those skilled in the artfrom the foregoing descriptions. Such modifications and variations areintended to fall within the scope of the appended claims. The presentdisclosure is to be limited only by the terms of the appended claims,along with the full scope of equivalents to which such claims areentitled. It is to be understood that this disclosure is not limited toparticular methods, reagents, compounds compositions or biologicalsystems, which can, of course, vary. It is also to be understood thatthe terminology used herein is for the purpose of describing particularembodiments only, and is not intended to be limiting.

In addition, where features or aspects of the disclosure are describedin terms of Markush groups, those skilled in the art will recognize thatthe disclosure is also thereby described in terms of any individualmember or subgroup of members of the Markush group.

As will be understood by one skilled in the art, for any and allpurposes, particularly in terms of providing a written description, allranges disclosed herein also encompass any and all possible subrangesand combinations of subranges thereof. Any listed range can be easilyrecognized as sufficiently describing and enabling the same range beingbroken down into at least equal halves, thirds, quarters, fifths,tenths, etc. As a non-limiting example, each range discussed herein canbe readily broken down into a lower third, middle third and upper third,etc. As will also be understood by one skilled in the art all languagesuch as ‘up to,’ ‘at least,’ ‘greater than,’ ‘less than,’ and the like,include the number recited and refer to ranges which can be subsequentlybroken down into subranges as discussed above. Similarly, the phrase “atleast about” some value such as, e.g., wt % includes at least the valueand about the value. For example “at least about 1 wt %” means “at least1 wt % or about 1 wt %.” Finally, as will be understood by one skilledin the art, a range includes each individual member.

While certain embodiments have been illustrated and described, it shouldbe understood that changes and modifications can be made therein inaccordance with ordinary skill in the art without departing from thetechnology in its broader aspects as defined in the following claims.

What is claimed is:
 1. A polymer comprising a linker represented byFormula I:

wherein: R¹ and R² are, independently, alkylene, alkenylene, arylene,heteroarylene, or alkylarylalkylene; the polymer has a weight averagemolecular weight of about 500 g/mol to about 2,000,000 g/mol; and m is 1to
 1000. 2. The polymer of claim 1, wherein: R¹ is C₂-C₁₀ alkylene; andR² is a mixture of at least two of p-xylenyl, m-xylenyl, and o-xylenyl.3. The polymer of claim 2, wherein R² is a mixture of p-xylenyl andm-xylenyl having a p-xylenyl:m-xylenyl ratio of about 2:1 to about 20:1.4. The polymer of claim 2, wherein R² is a mixture of p-xylenyl ando-xylenyl having a p-xylenyl:o-xylenyl ratio of about 2:1 to about 20:1.5. The polymer of claim 1, wherein R¹ is (CH₂)₂; (CH₂)₄; (CH₂)₆; or(CH₂)₈.
 6. A polymer represented by Formula III:

wherein: A is hydrogen, alkyl, or —C(O)R⁴; R¹ and R² are, independently,alkylene, alkenylene, arylene, heteroarylene, or alkylarylalkylene; R⁴is hydrogen, alkyl, or phenyl; PG^(1a) is the polymerization product ofa polymerization group PG¹; PG¹ is selected from the group consisting ofacrylyl, methacrylyl, isocycanyl, styrenyl, epoxyl, vinyl, oxetanyl,DL-lactidyl, and bicyclo[2.2.1]hept-2-enyl; the polymer has a weightaverage molecular weight of about 500 g/mol to about 2,000,000 g/mol; mis 1 to 1000; and q is 1 to
 1000. 7. The polymer of claim 6, wherein: R¹is (CH₂)₂; (CH₂)₄; (CH₂)₆; or (CH₂)₈; and R² is a mixture of at leasttwo of p-xylenyl, m-xylenyl, and o-xylenyl.
 8. The polymer of claim 6,wherein m is 1 to
 50. 9. The polymer of claim 6, wherein q is 1 to 50.10. A method of preparing polymer represented by Formula III, the methodcomprising: contacting XCH₂OR²OCH₂X with HOR¹⁰H, HOR¹OA, and a base toform a polymer represented by Formula V:

contacting the polymer represented by Formula V with a compoundrepresented by PG¹-L and a base to form a polymer represented by FormulaVI:

and polymerizing PG¹ of the polymer represented by Formula VI to formthe polymer represented by Formula III:

wherein: A is hydrogen, alkyl, or —C(O)R⁴; R¹ and R² are, independently,alkylene, alkenylene, arylene, heteroarylene, or alkylarylalkylene; R⁴is hydrogen, alkyl, or phenyl; X is a leaving group; PG¹ is apolymerizable group selected from the group consisting of acrylyl,methacrylyl, isocycanyl, styrenyl, epoxyl, vinyl, oxetanyl, DL-lactidyl,and bicyclo[2.2.1]hept-2-enyl; PG^(1a) is the polymerization product ofthe polymerizable group PG¹; L is a leaving group; m is 1 to 1000; and qis 1 to
 1000. 11. The method of claim 10, wherein the polymerrepresented by Formula III is a polymer represented by Formula IV:

wherein: R⁵ is hydrogen, CN, alkyl, or phenyl.
 12. The method of claim10, further comprising forming XCH₂OR²OCH₂X by contactingR⁶OCH₂OR²OCH₂OR⁶ with HX, wherein R⁶ is alkyl.
 13. The method of claim12, wherein R⁶ is methyl.
 14. The method of claim 10, wherein X Cl, Br,I,

and L, Cl, Br, I,


15. The method of claim 14, wherein X and L are Cl.
 16. The method ofclaim 10, wherein the base is a tertiary amine, secondary amine,pyridine, or a carbonate salt.
 17. The method of claim 16, wherein thebase is morpholine, N-methylmorpholine, piperidine, N-methypiperidine,piperazine, N-methylpiperazine, N,N-dimethylpiperazine, triethylamine,diisopropylethylamine, or pyridine.